CN108604686B - Polymer compound, negative electrode, method for producing negative electrode, intermediate composition, electricity storage device, and slurry for negative electrode - Google Patents
Polymer compound, negative electrode, method for producing negative electrode, intermediate composition, electricity storage device, and slurry for negative electrode Download PDFInfo
- Publication number
- CN108604686B CN108604686B CN201780010508.1A CN201780010508A CN108604686B CN 108604686 B CN108604686 B CN 108604686B CN 201780010508 A CN201780010508 A CN 201780010508A CN 108604686 B CN108604686 B CN 108604686B
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- China
- Prior art keywords
- negative electrode
- polyacrylic acid
- polymer compound
- carboxyl groups
- lithium
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 107
- 229920000642 polymer Polymers 0.000 title claims abstract description 95
- 239000000203 mixture Substances 0.000 title claims description 88
- 238000003860 storage Methods 0.000 title claims description 42
- 239000002002 slurry Substances 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 230000005611 electricity Effects 0.000 title claims description 14
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 148
- 150000001412 amines Chemical class 0.000 claims abstract description 79
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 73
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 73
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 17
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims abstract description 16
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 15
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract description 15
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims description 54
- 238000010438 heat treatment Methods 0.000 claims description 52
- 239000012046 mixed solvent Substances 0.000 claims description 41
- 238000006138 lithiation reaction Methods 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000007773 negative electrode material Substances 0.000 claims description 32
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 31
- 229910052744 lithium Inorganic materials 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 28
- 125000003277 amino group Chemical group 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 16
- 238000005275 alloying Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
- 239000003575 carbonaceous material Substances 0.000 claims description 7
- 239000003125 aqueous solvent Substances 0.000 claims description 6
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 66
- 239000000243 solution Substances 0.000 description 35
- 239000007864 aqueous solution Substances 0.000 description 20
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 12
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 12
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 12
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 125000004018 acid anhydride group Chemical group 0.000 description 10
- 238000006482 condensation reaction Methods 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- -1 amine compound Chemical class 0.000 description 5
- 239000011883 electrode binding agent Substances 0.000 description 5
- 239000002210 silicon-based material Substances 0.000 description 5
- QHQSCKLPDVSEBJ-UHFFFAOYSA-N 1,3,5-tri(4-aminophenyl)benzene Chemical compound C1=CC(N)=CC=C1C1=CC(C=2C=CC(N)=CC=2)=CC(C=2C=CC(N)=CC=2)=C1 QHQSCKLPDVSEBJ-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
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- 125000005462 imide group Chemical group 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
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- CKOFBUUFHALZGK-UHFFFAOYSA-N 3-[(3-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC(CC=2C=C(N)C=CC=2)=C1 CKOFBUUFHALZGK-UHFFFAOYSA-N 0.000 description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- 238000001035 drying Methods 0.000 description 3
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
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- 239000010936 titanium Substances 0.000 description 3
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- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- JUQPZRLQQYSMEQ-UHFFFAOYSA-N CI Basic red 9 Chemical compound [Cl-].C1=CC(N)=CC=C1C(C=1C=CC(N)=CC=1)=C1C=CC(=[NH2+])C=C1 JUQPZRLQQYSMEQ-UHFFFAOYSA-N 0.000 description 2
- 229910004706 CaSi2 Inorganic materials 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004962 Polyamide-imide Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 229910052730 francium Inorganic materials 0.000 description 2
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- 229910052732 germanium Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002312 polyamide-imide Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
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- 229910052712 strontium Inorganic materials 0.000 description 2
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
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- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 1
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- RZVCEPSDYHAHLX-UHFFFAOYSA-N 3-iminoisoindol-1-amine Chemical compound C1=CC=C2C(N)=NC(=N)C2=C1 RZVCEPSDYHAHLX-UHFFFAOYSA-N 0.000 description 1
- XTEBLARUAVEBRF-UHFFFAOYSA-N 4-(1,1,1,3,3,3-hexafluoropropan-2-yl)aniline Chemical compound NC1=CC=C(C(C(F)(F)F)C(F)(F)F)C=C1 XTEBLARUAVEBRF-UHFFFAOYSA-N 0.000 description 1
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- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
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- 229910020968 MoSi2 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
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- XUYGNGMQMDMYHW-UHFFFAOYSA-N benzene-1,3-diamine Chemical compound NC1=CC=CC(N)=C1.NC1=CC=CC(N)=C1 XUYGNGMQMDMYHW-UHFFFAOYSA-N 0.000 description 1
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- DFJQEGUNXWZVAH-UHFFFAOYSA-N bis($l^{2}-silanylidene)titanium Chemical compound [Si]=[Ti]=[Si] DFJQEGUNXWZVAH-UHFFFAOYSA-N 0.000 description 1
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- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
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- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- MIROPXUFDXCYLG-UHFFFAOYSA-N pyridine-2,5-diamine Chemical compound NC1=CC=C(N)N=C1 MIROPXUFDXCYLG-UHFFFAOYSA-N 0.000 description 1
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical class [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Abstract
A polymer compound obtained by condensing polyacrylic acid having a part of carboxyl groups lithiated and a polyfunctional amine represented by the following general formula (1), wherein a chain structure of the polyacrylic acid has a free carboxyl group and a lithium-lithiated carboxyl group. Y is a linear alkyl group with 1-4 carbon atoms, a phenylene group or an oxygen atom, and R1 and R2 are respectively and independently a single or multiple hydrogen atoms, methyl, ethyl, trifluoromethyl or methoxy.
Description
Technical Field
The present invention relates to a polymer compound used as a binder for a negative electrode of an electricity storage device, an intermediate composition of the polymer compound, a negative electrode, an electricity storage device, a slurry for a negative electrode, a method for producing a polymer compound, and a method for producing a negative electrode.
Background
Products using the secondary battery are increasing. Secondary batteries are often used in portable devices such as mobile phones and notebook computers. Secondary batteries are also attracting attention as large-sized power sources for electric vehicles.
An electrode of a secondary battery includes a current collector formed of a metal material such as copper or aluminum, and an active material layer bonded to the current collector. The active material layer generally contains a binder (binder) for an electrode for binding the active material to the current collector. In recent years, polyacrylic acid, which is an inexpensive polymer compound, has been used as a binder for electrodes. For example, patent document 1 discloses a binder for an electrode containing a lithium polyacrylate salt and a sodium polyacrylate salt. Patent document 2 discloses a binder for an electrode comprising polyacrylic acid and polyethyleneimine. Patent document 3 discloses a binder for an electrode comprising polyacrylic acid and an amine compound.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2009-080971
Patent document 2: japanese laid-open patent publication No. 2009-135103
Patent document 3: japanese patent laid-open No. 2003-003031
Disclosure of Invention
Problems to be solved by the invention
The present inventors have intensively studied and found that a polymer compound obtained by condensing polyacrylic acid having a part of carboxyl groups lithiated and a polyfunctional amine having a specific molecular structure is useful as a binder for a negative electrode of an electric storage device such as a secondary battery. The purpose of the present invention is to provide a polymer compound useful as a binder for a negative electrode of an electricity storage device, an intermediate composition for obtaining the polymer compound, a negative electrode using the polymer compound as a binder for a negative electrode, an electricity storage device, and a slurry for a negative electrode. Further, the present invention aims to provide a method for producing the polymer compound and a method for producing a negative electrode.
Means for solving the problems
In order to solve the above problems, according to a first aspect of the present invention, there is provided a polymer compound used as a binder for a negative electrode of an electric storage device, which is obtained by condensing polyacrylic acid having a part of carboxyl groups salified with lithium and a polyfunctional amine represented by the following general formula (1), wherein a chain structure of the polyacrylic acid has a free carboxyl group and a carboxyl group lithiated,
[ chemical formula 1]
Y is a linear alkyl group having 1 to 4 carbon atoms, a phenylene group or an oxygen atom, and R1 and R2 are each independently a single or plural hydrogen atoms, methyl, ethyl, trifluoromethyl or methoxy.
In order to solve the above problems, according to a second aspect of the present invention, there is provided a polymer compound used as a binder for a negative electrode of an electric storage device, the polymer compound having a chain structure composed of polyacrylic acid and a crosslinked structure connecting carboxyl groups in or between the chain structure to each other, the crosslinked structure being at least one crosslinked structure selected from the following general formulae (2) to (4), the chain structure having a free carboxyl group and a carboxyl group lithiated,
[ chemical formula 2]
PAA represents a chain structure composed of polyacrylic acid salified with lithium, X represents a structure represented by the following general formula (5),
[ chemical formula 3]
Y is a linear alkyl group having 1 to 4 carbon atoms, a phenylene group or an oxygen atom, and R1 and R2 are each independently a hydrogen atom, a methyl group, a trifluoromethyl group or a methoxy group.
In order to solve the above problems, according to a third aspect of the present invention, there is provided an intermediate composition of a polymer compound used as a binder for a negative electrode of an electricity storage device, comprising: polyacrylic acid in which a part of the carboxyl groups is lithiated; a polyfunctional amine represented by the following general formula (1); and a mixed solvent of a non-aqueous solvent and water, polyacrylic acid and polyfunctional amine being dissolved in the mixed solvent,
[ chemical formula 4]
Y is a linear alkyl group having 1 to 4 carbon atoms, a phenylene group or an oxygen atom, and R1 and R2 are each independently a single or plural hydrogen atoms, methyl, ethyl, trifluoromethyl or methoxy.
In order to solve the above problems, according to a fourth aspect of the present invention, there is provided a method for producing a polymer compound, comprising heating polyacrylic acid having a part of carboxyl groups lithiated and a polyfunctional amine represented by the following general formula (1) in a mixed solvent of a nonaqueous solvent and water at 150 to 230 ℃,
[ chemical formula 5]
Y is a linear alkyl group with 1-4 carbon atoms, a phenylene group or an oxygen atom, and R1 and R2 are respectively and independently a single or multiple hydrogen atoms, methyl, ethyl, trifluoromethyl or methoxy.
In order to solve the above problem, according to a fifth aspect of the present invention, there is provided a negative electrode for a power storage device, including: a binder for a negative electrode containing the polymer compound; and a negative electrode active material which is at least one selected from a carbon-based material capable of absorbing and desorbing lithium, an element capable of alloying with lithium, and a compound having an element capable of alloying with lithium.
In order to solve the above problem, according to a sixth aspect of the present invention, there is provided a power storage device including: the above-described negative electrode; and a non-aqueous electrolyte.
In order to solve the above problem, according to a seventh aspect of the present invention, there is provided a slurry for a negative electrode, which is used for manufacturing a negative electrode of an electricity storage device, and which contains: the intermediate composition described above; and a negative electrode active material containing at least one substance selected from a carbon-based material capable of absorbing and desorbing lithium, an element capable of alloying with lithium, and a compound having an element capable of alloying with lithium.
In order to solve the above problems, according to an eighth aspect of the present invention, there is provided a method for manufacturing a negative electrode for a power storage device, wherein a negative electrode active material layer is formed on a current collector using the slurry for a negative electrode.
Detailed Description
The polymer compound of the present embodiment is a compound obtained by condensing (a) polyacrylic acid (lithiated polyacrylic acid) in which a part of carboxyl groups is lithiated and (B) polyfunctional amine.
(A) The lithiated polyacrylic acid is a compound obtained by lithiating a part of carboxyl groups of polyacrylic acid, which is a homopolymer including acrylic acid. (A) The lithium polyacrylic acid may be a commercially available product, or a product obtained by lithium-salifying (neutralizing) a part of the carboxyl groups of polyacrylic acid with a lithium compound such as lithium hydroxide, lithium carbonate, or organolithium.
The weight average molecular weight of the lithiated polyacrylic acid is not particularly limited, and is, for example, preferably in the range of 10,000 to 2,000,000, more preferably in the range of 25,000 to 1,800,000, and still more preferably in the range of 50,000 to 1,500,000, as a value in terms of lithium as a hydrogen atom.
Here, when a conventional polymer compound such as polyamideimide is used as a binder for a negative electrode, the cycle characteristics of the power storage device tend to decrease as the weight average molecular weight of the polymer compound decreases. When the polymer compound of the present embodiment is used as a binder for a negative electrode, the cycle characteristics of the power storage device are maintained even if the weight average molecular weight of polyacrylic acid constituting the polymer compound is reduced. Therefore, as the (a) lithiated polyacrylic acid, for example, a low molecular weight polyacrylic acid of 250,000 or less or 100,000 or less is preferably used.
(B) The polyfunctional amine is a compound having a structure represented by the following general formula (1).
[ chemical formula 6]
In the general formula (1), Y is a linear alkyl group having 1 to 4 carbon atoms, a phenylene group or an oxygen atom. The binding position of Y in each benzene ring may be any of the ortho, meta, and para positions with respect to the amino group.
When Y is a straight-chain alkyl group or a phenylene group, a substituent may be bonded to a carbon atom constituting the structure. Examples of the substituent bonded to a carbon atom constituting a linear alkyl group include a methyl group, an ethyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a methoxy group, an ethoxy group, and an oxo group. Only one of these substituents may be bonded, or two or more of them may be bonded. The number of substituents bonded to one carbon atom may be 1 or 2. The substituent bonded to the carbon atom constituting the linear alkyl group and the phenylene group may be an amino group or a substituent containing an amino group, and in this case, a polyfunctional amine having 3 or more amino groups is used.
In the general formula (1), R1 and R2 are each independently a single or plural hydrogen atom, methyl group, ethyl group, trifluoromethyl group or methoxy group. When R1 is a methyl group, an ethyl group, a trifluoromethyl group, or a methoxy group, the binding position of R1 may be any of the ortho-position, meta-position, and para-position with respect to the amino group. The same applies to R2.
Specific examples of the polyfunctional amine (B) are described.
Examples of the polyfunctional amine in which Y is a linear alkyl group include 3,3' -diaminodiphenylmethane, 4' -diaminodiphenylmethane, 3,4' -diaminodiphenylmethane, 4' -ethylenedianiline, 4' -diamino-3, 3' -dimethyldiphenylmethane, 1-bis (4-aminophenyl) cyclohexane, 9-bis (4-aminophenyl) fluorene, 2' -bis (4-aminophenyl) hexafluoropropane, 4' -diaminobenzophenone, 4' -methylenebis (2-ethyl-6-methylaniline) and parafuchsin.
Examples of the polyfunctional amine in which Y is a phenylene group include 1,3, 5-tris (4-aminophenyl) benzene. Examples of the polyfunctional amine in which Y is an oxygen atom include 4,4' -diaminodiphenyl ether. 1,3, 5-tris (4-aminophenyl) benzene and parafuchsin are trifunctional amines having 3 amino groups. Only one kind of the above polyfunctional amine may be used, or two or more kinds may be used simultaneously.
The blending ratio of the lithiated polyacrylic acid (a) and the polyfunctional amine (B) in the condensation is set according to the number of amino groups of the polyfunctional amine (B). That is, the blending ratio is set so that the total number of carboxyl groups not lithiated from the (a) lithiated polyacrylic acid is larger than the total number of amino groups from the (B) polyfunctional amine. In other words, the blending ratio is set so that the amount of the carboxyl group not lithiated in the (a) lithiated polyacrylic acid is 1 equivalent or more to 1 equivalent of the amino group in the (B) polyfunctional amine. The ratio (carboxyl/amino ratio) of the total number of non-lithiated carboxyl groups derived from (A) the lithiated polyacrylic acid to the total number of amino groups derived from (B) the polyfunctional amine is preferably in the range of 1 to 8, more preferably in the range of 2 to 6.
The polymer compound of the present embodiment can be obtained by a mixing step of mixing (a) lithiated polyacrylic acid and (B) polyfunctional amine in a solvent and a heating step of heating the intermediate composition obtained in the mixing step.
The mixing step is a step of obtaining a liquid intermediate composition in which (a) lithiated polyacrylic acid and (B) polyfunctional amine are mixed. As the solvent used in the mixing step, a mixed solvent of a nonaqueous solvent and water can be used.
Examples of the nonaqueous solvent constituting the mixed solvent include acetone, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene carbonate, γ -butyrolactone, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, acetonitrile, dimethyl sulfoxide, and ethylene glycol monobutyl ether. Only one kind of these nonaqueous solvents may be mixed, or two or more kinds may be mixed.
The mixing ratio of the nonaqueous solvent to water in the mixed solvent is set to a ratio at which the (a) lithiated polyacrylic acid and the (B) polyfunctional amine are dissolved (not precipitated). The mixing ratio is set according to the lithiation degree of (a) lithiated polyacrylic acid, which is obtained by the following formula, for example.
Degree of lithiation (%) ═ LC "/(" C "-" a ") × 100
"C": the total number of carboxyl groups from the lithiated polyacrylic acid (including carboxyl groups lithiated.)
"LC": the total number of lithiated carboxyl groups in the carboxyl groups from lithiated polyacrylic acids
"A": total number of amino groups from polyfunctional amines
For example, when the lithiation degree of the lithiated polyacrylic acid (a) is in the range of 5 to 50%, the mixing ratio of the nonaqueous solvent and water is preferably 2: 1-1: 2, in the above range. When the lithiation degree of the lithiated polyacrylic acid (a) is in the range of 50 to 75%, the mixing ratio of the nonaqueous solvent to water is preferably 1: 1-1: 2, in the above range.
The heating step is a step of condensing (a) lithiated polyacrylic acid and (B) polyfunctional amine contained in the intermediate composition by heating the intermediate composition. The heating temperature in the heating step is preferably in the range of 150 to 230 ℃, and more preferably in the range of 180 to 200 ℃ from the viewpoint of efficiently forming amide bonds and imide bonds between (a) the lithiated polyacrylic acid and (B) the polyfunctional amine. When the polymer compound of the present embodiment is used as a binder for a negative electrode, the characteristics (cycle characteristics) of an electric storage device such as a secondary battery are improved if the heating temperature is increased.
When the intermediate composition is heated, a catalyst may be added to the intermediate composition in order to perform a condensation reaction for forming an amide bond and an imide bond or to increase the reaction rate of the condensation reaction. As the above catalyst, dehydration condensation catalysts such as 1-methylimidazole, 2-methylimidazole, N ' -dicyclohexylcarbodiimide, N ' -carbonyldiimidazole, N ' -diisopropylcarbodiimide, 1- [3- (dimethylamino) propyl ] -3-ethylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, diphenylphosphorylazide, BOP reagent and the like can be effectively used. When these catalysts are added, an amide bond and an imide bond can be formed at a lower temperature, and thus the production efficiency of the polymer compound is improved.
Preferably, the intermediate composition is subjected to a preliminary heating treatment before the heating step. The preheating temperature is preferably in the range of 40-140 ℃, and more preferably in the range of 60-130 ℃. By the preliminary heating treatment, the lithiated polyacrylic acid (a) and the polyfunctional amine (B) contained in the intermediate composition are associated with each other, and a state in which a condensation reaction of a carboxyl group and an amino group is easily performed is formed. As a result, the condensation reaction proceeds efficiently in the heating step. The amide bond and the imide bond may be formed by partial condensation reaction of the carboxyl group and the amino group by the preliminary heating treatment.
In the case of using the intermediate composition after the preliminary heating treatment, the heating step is preferably performed in a state where the solvent contained in the intermediate composition is removed. In this case, the condensation reaction of (a) lithiated polyacrylic acid and (B) polyfunctional amine becomes easy to proceed.
Then, a polymer compound obtained by condensing (A) lithiated polyacrylic acid and (B) polyfunctional amine is obtained through a heating step. The polymer compound is considered to have a structure in which (a) the lithiated polyacrylic acid is crosslinked with each other by forming at least one of an amide bond and an imide bond between (a) the carboxyl group of the lithiated polyacrylic acid and (B) the amino group of the polyfunctional amine.
That is, the polymer compound has a chain structure composed of (a) lithiated polyacrylic acid and a cross-linked structure in which carboxyl groups in the chain structure or between the chain structures are connected to each other. In addition, free carboxyl groups and lithium-esterified carboxyl groups are present in a chain structure composed of (a) lithiated polyacrylic acid, and the crosslinked structure is at least one crosslinked structure selected from the following general formulae (2) to (4).
In the chain structure of (a) lithiated polyacrylic acid, the ratio of free carboxyl groups to lithium-esterified carboxyl groups (free carboxyl groups: lithium-salted carboxyl groups) is preferably 95: 5-25: 75, more preferably 95: 5-45: 55, in the above range.
[ chemical formula 7]
In general formulae (2) to (4), PAA represents a chain structure composed of lithiated polyacrylic acid. X is a structure represented by the following general formula (5). In the general formulae (3) to (4) having an imide structure, the 2 carbonyl groups constituting one imide structure may be carbonyl groups bonded to different chain structures, respectively, or carbonyl groups bonded to the same chain structure. For example, in the case where 2 carbonyl groups constituting an imide structure are carbonyl groups bonded to adjacent carbons in the same chain structure, a maleimide structure as an imide structure is formed.
[ chemical formula 8]
In the general formula (5), Y is a C1-4 linear alkyl group, a phenylene group or an oxygen atom. The binding position of Y in each benzene ring may be any of the ortho, meta, and para positions with respect to the amino group. Y in the general formula (5) is a structure based on Y in the general formula (1).
In the general formula (5), R1 and R2 are each independently a single or plural hydrogen atom, methyl group, ethyl group, trifluoromethyl group or methoxy group. When R1 is a methyl group, a trifluoromethyl group or a methoxy group, the binding position of R1 may be any of the ortho-position, meta-position or para-position with respect to the amino group. The same applies to R2. R1 and R2 in the general formula (5) are based on R1 and R2 in the general formula (1).
The polymer compound preferably has both an amide bond and an imide bond in its crosslinked structure. That is, the polymer compound preferably has at least the crosslinked structures of the general formulae (2) and (4) or at least the crosslinked structure of the general formula (3) as the crosslinked structure.
The polymer compound may have an acid anhydride structure (CO — O — CO) formed by dehydration condensation of 2 carboxyl groups in the molecular structure. The acid anhydride structure may be formed in the same chain structure (PAA) or may be formed between different chain structures (PAA). That is, the two carbonyl carbons included in the acid anhydride structure may be bonded to the same chain structure (PAA) or may be bonded to different chain Structures (PAAs).
The polymer compound of the present embodiment may further have a 2 nd crosslinked structure.
For example, the polymer compound further having the 2 nd crosslinked structure may be a polymer compound obtained by condensing (a) lithiated polyacrylic acid and (B) polyfunctional amine represented by the general formula (1) and other polyfunctional amine. In this case, the polymer compound has a 2 nd crosslinked structure derived from another polyfunctional amine in addition to the crosslinked structure derived from the polyfunctional amine represented by the general formula (1). By adding the 2 nd crosslinked structure, physical properties such as strength and flexibility of the polymer compound can be adjusted.
Examples of other polyfunctional amines include 1, 4-diaminobutane, 1, 6-diaminohexane, 1, 8-diaminooctane, 2-aminoaniline (1, 2-phenylenediamine), 3-aminoaniline (1, 3-phenylenediamine), 4-aminoaniline (1, 4-phenylenediamine), 2, 4-diaminopyridine, 2, 5-diaminopyridine, 2, 6-diaminopyridine and 1, 3-diiminoisoindoline.
The blending ratio of the other polyfunctional amines is preferably 1 part by mass or less with respect to 10 parts by mass of the polyfunctional amine represented by the general formula (1) of (B). By setting the above ratio, it is possible to suppress a large change in physical properties such as strength and flexibility of the polymer compound, and thus the polymer compound is no longer suitable for the negative electrode binder.
Next, an example of a method for producing a negative electrode using the polymer compound of the present embodiment as a binder for a negative electrode will be described.
First, a negative electrode active material, a negative electrode binder, and a solvent are mixed to prepare a slurry. At this time, other components such as a conductive assistant may be further mixed as necessary.
As the negative electrode active material, known materials used as a negative electrode active material for an electric storage device such as a secondary battery can be used, and for example, a carbon-based material, an element capable of alloying with lithium, and a compound having an element capable of alloying with lithium can be used.
Examples of the carbon-based material include carbon having a property of absorbing and desorbing lithium, and specific examples thereof include hard-to-graphitize carbon, natural graphite, artificial graphite, coke-based materials, graphite-based materials, glassy carbon-based materials, organic polymer compound-based sintered materials, carbon fibers, activated carbon, and carbon black-based materials.
Examples of the element capable of alloying with lithium include Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Ti, Ag, Zn, Cd, Al, Ga, In, Si, Ge, Sn, Pb, Sb, and Bi. Among them, Si is particularly preferable.
Examples of the element capable of alloying with lithium include compounds having an element selected from Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Ti, Ag, Zn, Cd, Al, Ga, In, Si, Ge, Sn, Pb, Sb, and Bi. Among them, a silicon-based material as a compound having Si is particularly preferable.
Examples of the silicon-based material include SiB4、SiB6、Mg2Si、Ni2Si、TiSi2、MoSi2、CoSi2、NiSi2、CaSi2、CrSi2、Cu5Si、FeSi2、MnSi2、NbSi2、TaSi2、VSi2、WSi2、ZnSi2、SiC、Si3N4、Si2N2O、SiOV(0＜V≤2)、SnSiO3And LiSiO. Among them, SiO is particularly preferableV(0＜V≤2)。
Further, as disclosed in International publication No. 2014/080608, CaSi can also be used2Silicon material obtained by decalcification reaction. The silicon material can be obtained by, for example, mixingFor CaSi2The layered polycrystalline silane obtained by acid (such as hydrochloric acid or hydrogen fluoride) treatment is decalcified (such as heating treatment at 300-1000 ℃). The polymer compound of the present embodiment is particularly preferably used in combination with a silicon-based material as a negative electrode active material having a large degree of expansion and contraction during charge and discharge. In addition, only one kind of the above-described negative electrode active material may be used, or two or more kinds may be used simultaneously.
The intermediate composition is used as a binder for a negative electrode to be mixed with the slurry.
In addition, other binders for negative electrodes may be used in combination. Examples of the binder for negative electrode include polyvinylidene fluoride, polytetrafluoroethylene, styrene-butadiene rubber, polyimide, polyamideimide, carboxymethyl cellulose, polyvinyl chloride, methacrylic resin, polyacrylonitrile, modified polyphenylene ether, polyethylene oxide, polyethylene, polypropylene, polyacrylic acid, and phenol resin.
Only one kind of these other binders for negative electrodes may be used at the same time, or two or more kinds may be used at the same time. When another binder for a negative electrode is used together, the solid content of the intermediate composition is preferably 1 mass% or more, more preferably 10 mass% or more, based on the total solid content of the binder for a negative electrode.
The mixing ratio of the negative electrode active material to the negative electrode binder (negative electrode active material: negative electrode binder) can be appropriately set depending on the types of the negative electrode active material and the negative electrode binder. The mixing ratio is preferably, for example, 5: 3-99: 1, more preferably 3: 1-97: 3, more preferably 16: 3-95: 5 in the above range.
The solvent is a mixed solvent of a non-aqueous solvent and water. The mixing ratio of the nonaqueous solvent and water in the mixed solvent is set to a ratio at which each component constituting the intermediate composition can be dissolved (not precipitated) in accordance with the degree of lithiation described above. Specific examples of the nonaqueous solvent and the mixing ratio according to the degree of lithiation are the same as those of the mixed solvent used in the mixing step. In addition, when the intermediate composition contains a sufficient amount of the mixed solvent as the slurry, the solvent may not be added at the time of adjusting the slurry.
As the conductive assistant, a known conductive assistant used for a negative electrode of an electric storage device such as a secondary battery can be used. Specific examples of the conductive assistant include acetylene black, carbon nanotubes, ketjen black, and the like. Only one kind of these conductive aids may be used, or two or more kinds may be used simultaneously.
When the conductive aid is contained in the slurry, it is preferable to contain a dispersant together with the conductive aid. Specific examples of the dispersant include polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl butyral, triazine compounds, and the like. Only one kind of these dispersants may be used, or two or more kinds may be used simultaneously.
Next, the slurry is applied to a current collector, and a negative electrode active material layer including the slurry is formed on the surface of the current collector. Then, the solvent contained in the negative electrode active material layer (the solvent of the slurry and the solvent contained in the intermediate composition) is removed, and the negative electrode active material layer is dried and heated to be cured. By this heat treatment, the lithiated polyacrylic acid (a) and the polyfunctional amine (B) contained in the intermediate composition are condensed, and the polymer compound of the present embodiment is formed in the negative electrode active material layer. The heat treatment may be performed in a state where the negative electrode active material layer contains a solvent, but is more preferably performed in a state where the negative electrode active material layer is dried.
Specific examples of the drying treatment and the heating treatment include heating under normal pressure or reduced pressure using a heat source such as hot air, infrared rays, microwaves, or high frequency waves. In the heat treatment, it is preferable to heat from the current collector side rather than from the negative electrode active material layer side. In addition, in the drying treatment, it is preferable to perform heating at a low temperature more slowly than to perform heating at a high temperature more rapidly, and in the heating treatment, it is preferable to perform heating at a high temperature more rapidly than to perform heating at a low temperature more slowly. By heating in this way, the initial efficiency and cycle characteristics of the power storage device can be improved.
As the current collector, a known metal material used as a current collector for a negative electrode of an electric storage device such as a secondary battery can be used. Examples of the metal material that can be used for the current collector include silver, copper, gold, aluminum, magnesium, tungsten, cobalt, zinc, nickel, iron, platinum, tin, indium, titanium, ruthenium, tantalum, molybdenum, and stainless steel.
A negative electrode using the polymer compound of the present embodiment as a binder for a negative electrode can be effectively used for a nonaqueous power storage device including a nonaqueous electrolyte as an electrolyte. Examples of the power storage device include a secondary battery, an electric double layer capacitor, and a lithium ion capacitor. Such a power storage device is useful as a nonaqueous secondary battery used for driving motors of electric vehicles and hybrid vehicles, personal computers, portable communication devices, household electric appliances, office equipment, industrial equipment, and the like.
Next, the effects of the present embodiment will be described.
(1) The polymer compound of the present embodiment is a compound obtained by condensing (a) lithiated polyacrylic acid and (B) polyfunctional amine, and the chain structure of the lithiated polyacrylic acid has a free carboxyl group and a lithium-esterified carboxyl group. The polymer compound of the present embodiment has a chain structure made of polyacrylic acid and a crosslinked structure in which carboxyl groups in the chain structure or between the chain structures are connected to each other, and the crosslinked structure is at least one crosslinked structure selected from the general formulae (2) to (4). The chain structure has a free carboxyl group and a lithium-esterified carboxyl group.
The polymer compound of the present embodiment is useful as a binder for a negative electrode of an electricity storage device. By using the polymer compound of the present embodiment as a binder for a negative electrode, the characteristics (cycle characteristics) of the power storage device can be improved. In particular, the cycle characteristics at low temperatures can be improved.
The following points are considered to be the main reasons why the characteristics of the power storage device are improved by using the polymer compound of the present embodiment as a binder for a negative electrode. That is, the polymer compound of the present embodiment has a structure in which a part of the carboxyl groups of the chain structure is lithiated. Therefore, the polarity of the polymer compound is higher than that of a polymer compound including polyacrylic acid or a polyacrylic acid derivative. In addition, the dielectric constant of the polymer compound becomes large due to the increase in polarity. Therefore, when the binder is used as a binder for a negative electrode, the barrier when lithium or the like moves inside the polymer compound is alleviated, and lithium or the like easily moves inside the polymer compound. As a result, the cycle characteristics of the power storage device are improved.
Other factors are considered to be the following. That is, when a polymer compound including polyacrylic acid or a derivative of polyacrylic acid is used as a binder for a negative electrode, carboxyl groups having a chain structure may be subjected to dehydration condensation with each other by heat treatment or the like performed during production of a negative electrode, thereby forming a crosslinked structure having an acid anhydride structure. Since the length of the crosslinked structure due to the acid anhydride structure is small, if the crosslinked structure is excessively formed, the chain structures are closely approached to each other, the polymer compound is stiffened, and the flexibility of the polymer compound is impaired.
In order to solve this problem, in the polymer compound of the present embodiment, a part of the carboxyl groups in the chain structure is lithiated, and thus the side chain cannot form an acid anhydride structure. This reduces the number of carboxyl groups capable of forming an acid anhydride structure, and suppresses excessive formation of a crosslinked structure of the acid anhydride structure.
Further, the flexibility of the polymer compound is ensured by suppressing the formation of a crosslinked structure due to an excessive formation of an acid anhydride structure. Thus, when used as a binder for a negative electrode, the binder has improved ability to follow volume changes due to expansion and contraction accompanying the absorption and desorption of lithium and the like. Further, by suppressing the formation of a crosslinked structure due to an excessive acid anhydride structure, the network structure of the polymer compound is suppressed from becoming too dense, and lithium or the like easily passes through the inside of the polymer compound. As a result, the cycle characteristics of the power storage device are improved.
(2) The polymer compound of the present embodiment as a binder for a negative electrode has a property of easily maintaining the cycle characteristics of the power storage device even if the weight average molecular weight is lower than that of a chain structure including polyacrylic acid. Therefore, even in the case of a low-molecular-weight polymer compound having a short chain structure portion, the polymer compound of the present embodiment can effectively function as a binder for a negative electrode. In addition, when a low-molecular-weight polymer compound is used as the binder for the negative electrode, a smaller amount of solvent can be used to prepare a slurry. Therefore, the solid content ratio of the slurry can be set to be large. This shortens the drying time for evaporating the solvent from the negative electrode active material layer when the negative electrode is manufactured, and therefore improves the productivity of the negative electrode. Therefore, when the polymer compound of the present embodiment is used as a binder for a negative electrode, productivity of the negative electrode can be easily improved.
(3) In the partial structure of the crosslinked structure represented by the general formula (5), Y is a linear alkyl group having 1 to 4 carbon atoms, a phenylene group, or an oxygen atom.
According to the above configuration, since the polymer compound has a local structure capable of moving within the crosslinked structure, the stretchability of the polymer compound is improved. Thus, the binder for a negative electrode using the polymer compound of the present embodiment easily follows volume changes due to expansion and contraction accompanying the absorption and release of lithium or the like. As a result, the characteristics of the power storage device are improved.
(4) An intermediate composition of a polymer compound contains (A) lithiated polyacrylic acid, (B) polyfunctional amine, and a mixed solvent of a nonaqueous solvent and water, wherein the (A) lithiated polyacrylic acid and the (B) polyfunctional amine are dissolved in the mixed solvent. And, when the lithiation degree is in the range of 5 to 50%, the mixing ratio of the nonaqueous solvent and water in the mixed solvent is 2: 1-1: 2, and when the lithiation degree is in the range of 50 to 75%, the mixing ratio of the nonaqueous solvent to water in the mixed solvent is 1: 1-1: 2, in the above range.
With the above configuration, the precipitation of components constituting the intermediate composition in the mixed solvent can be suppressed. As a result, the polymer compound of the present embodiment can be obtained efficiently. In addition, when a negative electrode is produced from a slurry in which the intermediate composition and the negative electrode active material are mixed, the polymer compound (binder for a negative electrode) obtained from the intermediate composition is suppressed from being non-uniform in the negative electrode.
That is, the precipitation of a component constituting the intermediate composition in the mixed solvent means that the component is aggregated. When a polymer compound is obtained by condensing an intermediate composition in which a part of components is precipitated by heating, it is difficult to perform a condensation reaction in a portion where the components are aggregated, and the yield of the target polymer compound is lowered. In addition, in the case where the negative electrode is produced using the intermediate composition in which a part of the components is precipitated, the target polymer compound cannot be sufficiently formed in the portion where the components are aggregated. Therefore, in the obtained negative electrode, a portion in which the polymer compound serving as the binder for the negative electrode is not sufficiently present is likely to be generated. In this regard, according to the above configuration, since the precipitation of the components constituting the intermediate composition in the mixed solvent is suppressed, the occurrence of the above-described problems can be suppressed when obtaining the polymer compound and when manufacturing the negative electrode.
Examples
Hereinafter, examples will be described in which the above embodiments are further embodied.
< test 1 >
Battery characteristics of the power storage device were evaluated when a polymer compound obtained by condensing a lithiated polyacrylic acid and a polyfunctional amine having a specific molecular structure was used as a binder for a negative electrode.
In addition, polyacrylic acid is hereinafter referred to as "PAA", and N-methyl-2-pyrrolidone is hereinafter referred to as "NMP".
(example 1A: PAA +4,4' -diaminodiphenylmethane, degree of lithiation 10%)
PAA having a weight average molecular weight of 50,000 was dissolved in water to prepare a 30 mass% aqueous solution of PAA, and 10g (41.6 mmol in terms of PAA monomer) of the aqueous solution of PAA was taken out from the flask under a nitrogen atmosphere. Lithium hydroxide monohydrate 0.131mg (3.12mmol) was added to the flask, and the mixture was stirred at room temperature for 30 minutes, thereby lithiating a part of the carboxyl group of PAA contained in the PAA aqueous solution. Further, 1.03g (5.19mmol) of 4,4' -diaminodiphenylmethane was dissolved in NMP14g to prepare a polyfunctional amine/NMP solution. The polyfunctional amine/NMP solution was added dropwise to the flask, and the mixture was stirred at room temperature for 30 minutes. Then, the intermediate composition of example 1A was obtained as a solution in a mixed solvent of NMP and water (NMP: water: 2: 1) by performing heat treatment (preliminary heat treatment) at 110 ℃ for 2 hours using a dean-stark apparatus. The lithiation degree of the intermediate composition of example 1 can be calculated by the following formula, and its value is 10%.
Lithium hydroxide monohydrate in terms of the number of moles/{ (PAA monomer-equivalent moles) - (number of polyfunctional amine moles) × (number of amino groups of polyfunctional amine) } × 100
(example 1B: PAA +4,4' -diaminodiphenylmethane, degree of lithiation 20%)
An intermediate composition of example 1B was obtained in the form of a solution by the same method as in example 1A, except that the amount of lithium hydroxide monohydrate added was changed to 0.262mg (6.24 mmol). The intermediate composition of example 1B had a degree of lithiation of 20%.
(example 1C: PAA +4,4' -diaminodiphenylmethane, degree of lithiation 50%)
An intermediate composition of example 1C was obtained in the form of a solution by the same method as in example 1A, except that the amount of lithium hydroxide monohydrate added was changed to 0.655mg (15.6 mmol). The intermediate composition of example 1C had a degree of lithiation of 50%.
(reference example 1: PAA +4,4' -diaminodiphenylmethane, degree of lithiation 0%)
PAA having a weight-average molecular weight of 50,000 was dissolved in NMP to prepare a 30 mass% PAA/NMP solution, and 10g (41.6 mmol in terms of PAA monomer) of the PAA/NMP solution was collected in a flask under a nitrogen atmosphere. Further, 1.03g (5.19mmol) of 4,4' -diaminodiphenylmethane was dissolved in NMP14g to prepare a polyfunctional amine/NMP solution. The polyfunctional amine/NMP solution was added dropwise to the flask, and the mixture was stirred at room temperature for 30 minutes. Then, heat treatment (preliminary heat treatment) was performed at 110 ℃ for 2 hours using a dean-stark apparatus, thereby obtaining an intermediate composition of reference example 1 in a state of a solution. The intermediate composition of reference example 1 had a degree of lithiation of 0%.
(reference example 2: PAA +1, 6-diaminohexane, degree of lithiation 10%)
PAA having a weight average molecular weight of 50,000 was dissolved in water to prepare a 30 mass% aqueous solution of PAA, and 10g (41.6 mmol in terms of PAA monomer) of the aqueous solution of PAA was taken out from the flask under a nitrogen atmosphere. Lithium hydroxide monohydrate 0.131mg (3.12mmol) was added to the flask, and the mixture was stirred at room temperature for 30 minutes, thereby lithiating a part of the carboxyl group of PAA contained in the PAA aqueous solution. Further, 0.603g (5.19mmol) of 1, 6-diaminohexane was dissolved in NMP14g to prepare a polyfunctional amine/NMP solution. The polyfunctional amine/NMP solution was added dropwise to the flask, and the mixture was stirred at room temperature for 30 minutes. Then, heat treatment (preliminary heat treatment) was performed at 110 ℃ for 2 hours using a dean-stark apparatus, thereby obtaining an intermediate composition of reference example 2 in a state of a solution. The intermediate composition of reference example 2 had a degree of lithiation of 10%.
(preparation of electrode slice)
Using the intermediate compositions of the obtained examples, electrode sheets were produced using the polymer compounds obtained from the respective intermediate compositions as binders for negative electrodes. Then, a lithium ion secondary battery was produced using the obtained electrode sheet, and the battery characteristics of the lithium ion secondary battery were evaluated.
85 parts by mass of SiO, 5 parts by mass of acetylene black, and 10 parts by mass of each solution of the intermediate composition were mixed, and a slurry was prepared by adding an arbitrary mixed solvent of NMP and water to the mixture. The slurry was applied to the surface of a 20 μm electrolytic copper foil (current collector) in a thin film form by a doctor blade method. Then, NMP in the slurry was volatilized and removed, thereby forming a negative electrode active material layer on the electrolytic copper foil. Then, the electrolytic copper foil and the negative electrode active material layer were compressed using a roll press machine so that the thickness of the negative electrode active material layer was 20 μm, whereby the electrolytic copper foil and the negative electrode active material layer were firmly adhered and joined.
Then, the negative electrode active material layer in a dried state from which NMP was removed was subjected to a heating treatment at 200 ℃ for 2 hours in a vacuum (under reduced pressure), thereby causing a condensation reaction of an intermediate composition contained in the negative electrode active material layer and heat-curing the negative electrode active material layer. Thus, an electrode sheet containing a polymer compound having a crosslinked structure as a binder for a negative electrode was obtained.
In addition, similar electrode sheets were produced using the aqueous solutions of the intermediate compositions of the respective reference examples or PAA instead of the aqueous solutions of the intermediate compositions of the examples.
(production of lithium ion Secondary Battery)
A separator was disposed between a negative electrode (evaluation electrode) obtained by cutting an electrode sheet into a circular shape having a diameter of 11mm and a positive electrode obtained by cutting a metal lithium foil having a thickness of 500 μm into a circular shape having a diameter of 13mm, thereby producing an electrode body battery. The electrode body battery was housed in a battery case, and a nonaqueous electrolyte was injected, and then the battery case was closed, thereby obtaining a lithium ion secondary battery. Further, as the separator, a glass filter manufactured by Herstein Salarnis and a Celgard2400 manufactured by Celgard were used. The nonaqueous electrolyte is used in a state that ethylene carbonate and diethyl carbonate are mixed in a volume ratio of 1: 1a nonaqueous electrolyte obtained by dissolving lithium hexafluorophosphate in a concentration of 1M in the mixed solvent.
(evaluation of Battery characteristics)
The obtained lithium ion secondary battery was discharged with a direct current of 0.2mA until the voltage of the negative electrode with respect to the positive electrode became 0.01V, and was charged with a direct current of 0.2mA until the voltage of the negative electrode with respect to the positive electrode became 1.0V after 10 minutes from the end of the discharge. The discharge capacity at this time was set as an initial discharge capacity, and the charge capacity was set as an initial charge capacity. Then, the initial efficiency was calculated based on the following equation. Table 1 shows the results.
Initial efficiency (%) - (initial charge capacity/initial discharge capacity) × 100
Further, the cycle characteristics were calculated based on the following formula by performing charge and discharge at 0 ℃ or 25 ℃ for a predetermined cycle with the above-described discharge and charge as 1 cycle. Table 1 shows the results.
Cycle characteristic (%) (charge capacity after predetermined cycle/initial charge capacity) × 100
[ Table 1]
As shown in table 1, it was confirmed that the cycle characteristics at 25 ℃ were evaluated more in test examples 1 to 5 in which a polymer compound having a crosslinked structure formed by condensing a polyfunctional amine was used as a binder for a negative electrode, than in test example 6 in which PAA was used as a binder for a negative electrode.
Furthermore, it was confirmed that, among the polymer compounds having a cross-linked structure formed by condensation of polyfunctional amines, in examples 1 to 3 in which a polymer compound obtained by condensation of PAA having a part of carboxyl groups lithiated and a polyfunctional amine having a specific molecular structure was used as a binder for a negative electrode, the evaluation of initial efficiency and cycle characteristics was higher than in example 4 in which PAA not lithiated and example 5 in which a polyfunctional amine having no specific molecular structure was used. In particular, in test examples 1 to 5, the cycle characteristics at low temperatures (0 ℃ C.) were also evaluated, and it was confirmed that the cycle characteristics at low temperatures (0 ℃ C.) in test examples 1 to 3 were greatly improved.
From these results, it is found that, among polymer compounds having a crosslinked structure formed by condensing polyfunctional amines, a polymer compound obtained by condensing PAA having a part of carboxyl groups salified with lithium and polyfunctional amine having a specific molecular structure is useful as a binder for a negative electrode of an electric storage device.
< test 2 >
Next, when a polymer compound obtained by condensing lithiated PAA and a polyfunctional amine having a specific molecular structure is used as a binder for a negative electrode, changes in battery characteristics of the power storage device when the polyfunctional amine is different in kind are evaluated.
(example 2: PAA +4,4' -diaminodiphenyl ether, degree of lithiation 10%)
PAA having a weight average molecular weight of 50,000 was dissolved in water to prepare a 30 mass% aqueous solution of PAA, and 10g (41.6 mmol in terms of PAA monomer) of the aqueous solution of PAA was taken out from the flask under a nitrogen atmosphere. Lithium hydroxide monohydrate 0.131mg (3.12mmol) was added to the flask, and the mixture was stirred at room temperature for 30 minutes, thereby lithiating a part of the carboxyl group of PAA contained in the PAA aqueous solution. Separately, 1.039g (5.19mmol) of 4,4' -diaminodiphenyl ether was dissolved in NMP14g to prepare a polyfunctional amine/NMP solution. The polyfunctional amine/NMP solution was added dropwise to the flask, and the mixture was stirred at room temperature for 30 minutes. Then, heat treatment (preliminary heat treatment) was performed at 110 ℃ for 2 hours using a dean-stark apparatus, whereby an intermediate composition of example 2 was obtained in a state of a solution. The intermediate composition of example 2 had a degree of lithiation of 10%.
(example 3: PAA +1,3, 5-tris (4-aminophenyl) benzene, degree of lithiation 10%)
PAA having a weight average molecular weight of 50,000 was dissolved in water to prepare a 30 mass% aqueous solution of PAA, and 10g (41.6 mmol in terms of PAA monomer) of the aqueous solution of PAA was taken out from the flask under a nitrogen atmosphere. Lithium hydroxide monohydrate 0.131mg (3.12mmol) was added to the flask, and the mixture was stirred at room temperature for 30 minutes, thereby lithiating a part of the carboxyl group of PAA contained in the PAA aqueous solution. Separately, 1.824g (5.19mmol) of 1,3, 5-tris (4-aminophenyl) benzene was dissolved in NMP14g to prepare a polyfunctional amine/NMP solution. The polyfunctional amine/NMP solution was added dropwise to the flask, and the mixture was stirred at room temperature for 30 minutes. Then, heat treatment (preliminary heat treatment) was performed at 110 ℃ for 2 hours using a dean-stark apparatus, whereby an intermediate composition of example 3 was obtained in a state of a solution. The intermediate composition of example 3 had a degree of lithiation of 10%.
(example 4: PAA +3,3' -diaminodiphenylmethane, degree of lithiation 10%)
PAA having a weight average molecular weight of 50,000 was dissolved in water to prepare a 30 mass% aqueous solution of PAA, and 10g (41.6 mmol in terms of PAA monomer) of the aqueous solution of PAA was taken out from the flask under a nitrogen atmosphere. Lithium hydroxide monohydrate 0.131mg (3.12mmol) was added to the flask, and the mixture was stirred at room temperature for 30 minutes, thereby lithiating a part of the carboxyl group of PAA contained in the PAA aqueous solution. Further, 1.029g (5.19mmol) of 3,3' -diaminodiphenylmethane was dissolved in NMP14g to prepare a polyfunctional amine/NMP solution. The polyfunctional amine/NMP solution was added dropwise to the flask, and the mixture was stirred at room temperature for 30 minutes. Then, heat treatment (preliminary heat treatment) was performed at 110 ℃ for 2 hours using a dean-stark apparatus, whereby an intermediate composition of example 4 was obtained in a state of a solution. The intermediate composition of example 4 had a degree of lithiation of 10%.
(example 5: PAA +4,4' -Dianilinyleneethylene, degree of lithiation 10%)
PAA having a weight average molecular weight of 50,000 was dissolved in water to prepare a 30 mass% aqueous solution of PAA, and 10g (41.6 mmol in terms of PAA monomer) of the aqueous solution of PAA was taken out from the flask under a nitrogen atmosphere. Lithium hydroxide monohydrate 0.131mg (3.12mmol) was added to the flask, and the mixture was stirred at room temperature for 30 minutes, thereby lithiating a part of the carboxyl group of PAA contained in the PAA aqueous solution. Separately, 1.101g (5.19mmol) of 4,4' -diphenylethylene was dissolved in NMP14g to prepare a polyfunctional amine/NMP solution. The polyfunctional amine/NMP solution was added dropwise to the flask, and the mixture was stirred at room temperature for 30 minutes. Then, heat treatment (preliminary heat treatment) was performed at 110 ℃ for 2 hours using a dean-stark apparatus, whereby an intermediate composition of example 5 was obtained in a state of a solution. The intermediate composition of example 5 had a degree of lithiation of 10%.
(evaluation of Battery characteristics)
Using the obtained intermediate compositions of examples 2 to 5, electrode sheets were produced using the polymer compounds obtained from the respective intermediate compositions as binders for negative electrodes. Further, a lithium ion secondary battery was produced using the obtained electrode sheet, and the battery characteristics of the lithium ion secondary battery were evaluated. The results are shown in Table 2. The methods for producing the electrode sheet and the lithium ion secondary battery and for evaluating the battery characteristics of the lithium ion secondary battery were the same as those in test 1.
[ Table 2]
As shown in table 2, even when the types of polyfunctional amines were different, it was confirmed that the same battery characteristics were obtained as compared with test example 1 using 4,4' -diaminodiphenylmethane.
< test 3 >
Next, with respect to an intermediate composition containing lithiated PAA, a polyfunctional amine having a specific molecular structure, and a mixed solvent of a nonaqueous solvent and water, changes in solubility when the degree of lithiation and the mixing ratio of the mixed solvent were made different were evaluated.
PAA having a weight average molecular weight of 50,000 was dissolved in water or NMP to prepare a 30 mass% PAA solution, and 10g (41.6 mmol in terms of PAA monomer) of the PAA solution was collected in a flask under a nitrogen atmosphere. A specific amount of lithium hydroxide monohydrate was added to the flask, and stirred at room temperature for 30 minutes, thereby lithiating a part of the carboxyl group of PAA contained in the PAA solution. Further, 1.03g (5.19mmol) of 4,4' -diaminodiphenylmethane was dissolved in a specific amount of NMP or water to prepare a polyfunctional amine solution. The polyfunctional amine solution was added dropwise to the flask, and the mixture was stirred at room temperature for 30 minutes. Then, heat treatment (preliminary heat treatment) was performed at 110 ℃ for 2 hours using a dean-stark apparatus, thereby obtaining an intermediate composition in the state of a solution with respect to a mixed solvent of NMP and water.
The amount of lithium hydroxide monohydrate added was adjusted so that the lithiation degree became the value shown in table 3. The amount of lithium hydroxide monohydrate added when the degree of lithiation was 0% was 0 g. The kinds of solvents constituting the PAA solution and the polyfunctional amine solution and the amount of the solvent used for dissolving 4,4' -diaminodiphenylmethane were adjusted so that the mixing ratio (mass ratio) of NMP to water in the mixed solvent included in the obtained intermediate composition became the values shown in table 3.
Table 3 shows the results, in table 3, the respective components constituting the intermediate composition were completely dissolved in the mixed solvent, the case where no precipitate was observed in the mixed solvent was designated as "○", any one of the components constituting the intermediate composition was insoluble in the mixed solvent, and the case where a precipitate was observed in the mixed solvent was designated as "x".
[ Table 3]
As shown in table 3, the following tendency was confirmed: the mixed solvent becomes insoluble in water at a large ratio as the degree of lithiation becomes lower, and becomes insoluble in NMP at a large ratio as the degree of lithiation becomes higher. When the degree of lithiation is 100%, the mixed solvent is insoluble in all mixing ratios.
From the above results, it is found that in order to obtain an intermediate composition in which the components constituting the intermediate composition are dissolved in the mixed solvent, the mixing ratio of NMP (nonaqueous solvent) and water in the mixed solvent needs to be set to a specific range depending on the degree of lithiation. Specifically, when the degree of lithiation is 50% or less, it is considered that the mixing ratio of NMP (nonaqueous solvent) and water in the mixed solvent is preferably 2: 1-1: 2, when the degree of lithiation is 50% or more, the mixing ratio of NMP (nonaqueous solvent) and water in the mixed solvent is preferably 1: 1-1: 2, in the above range.
< test 4 >
Next, the intermediate composition of example 1B (PAA +4,4 '-diaminodiphenylmethane, degree of lithiation 20%) and the intermediate composition of reference example 1 (PAA +4,4' -diaminodiphenylmethane, degree of lithiation 0%) were analyzed for changes in the molecular structure due to heat treatment by thermal scanning infrared spectroscopy.
First, a disk-shaped substrate having a diameter of 10mm was formed from calcium fluoride pulverized in a mortar. Next, about 10 μ l of the solution of the intermediate composition of example 1B or reference example 1 was dropped onto one surface of the substrate under an argon atmosphere, and the substrate was left to stand for 24 hours to be dried, and then left to stand in vacuum (under reduced pressure) for 1 hour to be further dried. Thus, a measurement sample having a layer of the intermediate composition having a thickness of about 5 μm on one surface of the substrate of calcium fluoride was prepared. The preparation of the measurement sample was all performed at room temperature. Then, while heating the obtained measurement sample under the circulation of helium gas, thermal scanning infrared spectrometry (transmission method) was performed at each temperature of 30 ℃, 110 ℃, 150 ℃, 180 ℃ (immediately after), 180 ℃ (after 30 minutes holding), 180 ℃ (after 2 hours holding), 200 ℃ (immediately after), and 200 ℃ (after 2 hours holding).
A measuring device: fourier transform Infrared Spectrophotometer Cary670 (manufactured by Agilent Technologies Co., Ltd.)
Measuring temperature: the temperature was raised from room temperature to 180 ℃ at a temperature raising rate of 5 ℃ per minute, and the temperature was maintained at 180 ℃ for 2 hours. Then, the temperature was increased from 180 ℃ to 200 ℃ at a rate of 5 ℃ per minute, and the temperature was maintained at 200 ℃ for 2 hours.
Resolution ratio: 4cm-1
And (4) accumulating times: 512 times (twice)
Wave number range: 4000-400 cm-1(MCT Detector)
Window material: KBr (lower limit of infrared transmission 400 cm)-1)
It is considered that only 1583cm, which was confirmed in the IR spectrum obtained with respect to the intermediate composition of example 1B, was obtained by comparison with the IR spectrum obtained with respect to the intermediate composition of reference example 1-1The adjacent peak represents a carboxyl group (COO) after lithium salt formation-) Peak of (2). And, the 1583cm-1The intensity of the peak in the vicinity is approximately constant at each measurement temperature from room temperature to 200 ℃. From these results, it is understood that the carboxyl group after lithium salification is present as it is in the process of the heat treatment (condensation reaction of the carboxyl group and the amino group) for causing the condensation reaction of the intermediate composition and after the heat treatment.
Claims (10)
1. A polymer compound used as a binder for a negative electrode of an electricity storage device, characterized in that,
is obtained by condensing polyacrylic acid having a part of carboxyl groups lithiated and a polyfunctional amine represented by the following general formula (1),
the chain structure of the polyacrylic acid has free carboxyl groups and lithium-esterified carboxyl groups,
[ chemical formula 1]
Y is a linear alkyl group having 1 to 4 carbon atoms, a phenylene group or an oxygen atom, and R1 and R2 are each independently a single or plural hydrogen atoms, methyl, ethyl, trifluoromethyl or methoxy.
2. A polymer compound used as a binder for a negative electrode of an electricity storage device, characterized in that,
having a chain structure of polyacrylic acid and a cross-linking structure for linking carboxyl groups in or between the chain structures,
the crosslinked structure is at least one crosslinked structure selected from the following general formulae (2) to (4),
the chain structure has free carboxyl groups and lithium-esterified carboxyl groups,
[ chemical formula 2]
PAA represents a chain structure composed of polyacrylic acid salified with lithium, X represents a structure represented by the following general formula (5),
[ chemical formula 3]
Y is a linear alkyl group having 1 to 4 carbon atoms, a phenylene group or an oxygen atom, and R1 and R2 are each independently a hydrogen atom, a methyl group, a trifluoromethyl group or a methoxy group.
3. The polymer compound according to claim 1 or 2,
the ratio of the free carboxyl groups to the lithium-esterified carboxyl groups was 95: 5-25: 75, in the above range.
4. An intermediate composition of a polymer compound used as a binder for a negative electrode of an electricity storage device, characterized in that,
comprises the following components: polyacrylic acid in which a part of the carboxyl groups is lithiated; a polyfunctional amine represented by the following general formula (1); and a mixed solvent of a non-aqueous solvent and water,
the polyacrylic acid and the polyfunctional amine are dissolved in the mixed solvent,
[ chemical formula 4]
Y is a linear alkyl group having 1 to 4 carbon atoms, a phenylene group or an oxygen atom, R1 and R2 are each independently a single or plural hydrogen atoms, a methyl group, an ethyl group, a trifluoromethyl group or a methoxy group,
the total number of carboxyl groups derived from the polyacrylic acid is represented by "C",
the total number of lithium-salified carboxyl groups among the carboxyl groups derived from the polyacrylic acid is referred to as "LC",
when the total number of amino groups derived from the polyfunctional amine is defined as "A",
the lithiation degree obtained by "" LC "/(" C "-" A "). times.100" "is in the range of 5 to 50%,
the mixing ratio of the non-aqueous solvent to water in the mixed solvent is 2: 1-1: 2, in the above range.
5. An intermediate composition of a polymer compound used as a binder for a negative electrode of an electricity storage device, characterized in that,
comprises the following components: polyacrylic acid in which a part of the carboxyl groups is lithiated; a polyfunctional amine represented by the following general formula (1); and a mixed solvent of a non-aqueous solvent and water,
the polyacrylic acid and the polyfunctional amine are dissolved in the mixed solvent,
[ chemical formula 4]
Y is a linear alkyl group having 1 to 4 carbon atoms, a phenylene group or an oxygen atom, R1 and R2 are each independently a single or plural hydrogen atoms, a methyl group, an ethyl group, a trifluoromethyl group or a methoxy group,
the total number of carboxyl groups derived from the polyacrylic acid is represented by "C",
the total number of lithium-salified carboxyl groups among the carboxyl groups derived from the polyacrylic acid is referred to as "LC",
when the total number of amino groups derived from the polyfunctional amine is defined as "A",
the lithiation degree obtained by "" LC "/(" C "-" A "). times.100" "is in the range of 50 to 75%,
the mixing ratio of the non-aqueous solvent to water in the mixed solvent is 1: 1-1: 2, in the above range.
6. A method for producing a polymer compound according to claim 2 or 3, wherein the polymer compound is produced by a polymerization method,
heating polyacrylic acid having a part of carboxyl groups lithiated and a polyfunctional amine represented by the following general formula (1) in a mixed solvent of a nonaqueous solvent and water at 150 to 230 ℃,
[ chemical formula 5]
Y is a linear alkyl group with 1-4 carbon atoms, a phenylene group or an oxygen atom, and R1 and R2 are respectively and independently a single or multiple hydrogen atoms, methyl, ethyl, trifluoromethyl or methoxy.
7. A negative electrode for an electric storage device, characterized in that,
the disclosed device is provided with: a binder for a negative electrode containing the polymer compound according to any one of claims 1 to 3; and a negative electrode active material,
the negative electrode active material is at least one selected from a carbon-based material capable of absorbing and desorbing lithium, an element capable of alloying with lithium, and a compound having an element capable of alloying with lithium.
8. An electric storage device is characterized in that,
the disclosed device is provided with: the negative electrode of claim 7; and a non-aqueous electrolyte.
9. A slurry for a negative electrode, which is used for producing a negative electrode of an electricity storage device,
comprises the following components: the intermediate composition of claim 4 or 5; and a negative electrode active material,
the negative electrode active material contains at least one substance selected from a carbon-based material capable of absorbing and desorbing lithium, an element capable of alloying with lithium, and a compound having an element capable of alloying with lithium.
10. A method for manufacturing a negative electrode of an electric storage device, comprising,
a negative electrode active material layer formed using the slurry for a negative electrode according to claim 9 for a current collector.
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